CN102775786B - Graphene oxide/cyanate ester composite material and preparation method thereof - Google Patents
Graphene oxide/cyanate ester composite material and preparation method thereof Download PDFInfo
- Publication number
- CN102775786B CN102775786B CN 201210282395 CN201210282395A CN102775786B CN 102775786 B CN102775786 B CN 102775786B CN 201210282395 CN201210282395 CN 201210282395 CN 201210282395 A CN201210282395 A CN 201210282395A CN 102775786 B CN102775786 B CN 102775786B
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- cyanate ester
- composite material
- ester resin
- parts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Images
Abstract
The invention relates to a graphene oxide/cyanate ester composite material and a preparation method of the graphene oxide/cyanate ester composite material, which belongs to the field of advanced composite material technology. The graphene oxide/cyanate ester composite material is prepared by using 0.1-10 parts of hyperbranched polysiloxane-modified graphene oxide, 5-50 parts of epoxy active dilute and 100 parts of bisphenol A cyanate ester prepared by a casting molding method. In order to improve dispersibility of graphene oxide in cyanate ester resin and bonding strength between graphene oxide and cyanate ester resin, hyperbranched polysiloxane is used to modify graphene oxide to introduce active functional group epoxy groups onto the surface of graphene oxide, which can chemically react with the resin. Otherwise, the epoxy active dilute can chemically react with the resin and the epoxy groups on the surface of the graphene. Thus, compatibility and interface adhesion between graphene oxide and the resin are increased on one hand, and low viscosity is helpful to disperse graphene on the other hand. The prepared composite material has excellent performances and can meet the use requirements of cyanate ester resin in various fields.
Description
Technical field
The invention belongs to advanced compound materials science domain, relate to a kind of graphene oxide/cyanate ester resin composite material and preparation method thereof.
Background technology
Graphene oxide is by graphite oxidation ultrasonic dispersion, except the performance with Graphene excellence, its surface is with the functional group of the high reaction activities such as hydroxyl, carboxyl and epoxide group, can introduce organo-functional group on the Graphene surface by chemical reaction graphene oxide is carried out to modification, can not only improve the dispersiveness of graphene oxide, and give the function that graphene oxide is new.For example, make graphene oxide by sonioation method, then by acyl chloride reaction, 4-amino-benzene oxygen phthalonitrile is grafted on to the graphene oxide surface, make the nitrile modified graphene, and using that it makes nano composite material as filler and poly (arylene ether nitrile), find that Young's modulus, tensile strength, the pyrolysis temperature of matrix material all obviously improves.And for example, utilize vinyltriethoxysilane to be modified graphene oxide, and be mixed with out nano composite material with Low Density Polyethylene, found the barrier property of Graphene in polymkeric substance.
Hyperbranched polyorganosiloxane has low viscosity, high rheological variation, good solubility, and for the dispersiveness that improves graphene oxide provides favourable condition, particularly its molecular end exists Si-Cl, Si-H, Si-OH, Si-NH
2the isoreactivity group, be easy to carry out molecular designing according to different needs.But have not yet to see the report of modifying graphene oxide with hyperbranched polymerization.Therefore, the present invention utilizes hyperbranched polyorganosiloxane to the graphene oxide modifying surface, like this, not only can improve the dispersiveness of graphene oxide, and can improve the interface binding intensity of graphene oxide and resin.
Cyanate ester resin has excellent high heat resistance, good comprehensive mechanical property and extremely low water-intake rate, a kind of functional materials and the structured material that has had potentiality since twentieth century in aviation field, can be used for making the structural part of military affairs, Aeronautics and Astronautics, navigational field, such as wing, ship shell etc., also can be made into foam sandwich construction material commonly used in aerospace.Particularly bisphenol A cyanate ester resin is because of its unique molecular structure, there is more excellent mechanical property, wet-hot aging performance and electrical property and more be subject to investigator's extensive favor, but its cured article is more crisp, need to carry out the service requirements that toughening modifying could meet more occasions to it.
Summary of the invention
The technical problem solved
For fear of the deficiencies in the prior art part, the present invention proposes a kind of graphene oxide/cyanate ester resin composite material and preparation method thereof, the oxidation graphene oxide that uses a kind of hyperbranched polyorganosiloxane to modify carries out toughening modifying to bisphenol A cyanate ester resin, meets the service requirements of the multiple fields of cyanate ester resin.
Technical scheme
A kind of graphene oxide/cyanate ester resin composite material is characterized in that the massfraction of material component is: 0.1 ~ 10 part of graphene oxide, 5 ~ 50 epoxy active diluents and 100 parts of bisphenol A cyanate ester resin monomer that hyperbranched polyorganosiloxane is modified; The chemical substance structure formula of the graphene oxide that described hyperbranched polyorganosiloxane is modified is:
The chemical substance structure formula of bisphenol A cyanate ester resin monomer is:
Described epoxy active diluent is E-44 or E-51.
A kind of method for preparing described graphene oxide/cyanate ester resin composite material is characterized in that step is as follows:
Step 1: the graphite oxide of 0.1 ~ 10 part is joined in the tetrahydrofuran solution of 1 ~ 100 part of KH-560, drip the HCl aqueous solution that 1 ~ 50mL concentration is 1mol/L after ultrasonic dispersion 0.5h, then after 50 ~ 80 ℃ of stirring 4 ~ 7h, obtain hyperbranched polyorganosiloxane and modify graphene oxide;
Step 2: 0.1 ~ 10 part of hyperbranched polyorganosiloxane is modified in the epoxy active diluent that graphene oxide joins 5 ~ 50 parts, under the power of 40 ~ 70W, ultrasonic dispersion is after 0.5 ~ 3 hour, join 100 parts in the bisphenol A cyanate ester resin monomer of 80 ℃ of meltings, at 80 ~ 120 ℃ of lower prepolymerization 15 ~ 60min;
Step 3: pour in preheated mould, in the vacuum chamber of 120 ℃, after vacuumizing bubble removing, take out, then putting into air dry oven carries out the stage and heat up to solidify, curing process is 140 ℃/2h+160 ℃/2h+180 ℃/2h, then naturally cooling, after the demoulding, then obtain graphene oxide/cyanate ester resin composite material at 200 ℃ of lower aftertreatment 2h.
Beneficial effect
A kind of graphene oxide/cyanate ester resin composite material that the present invention proposes and preparation method thereof, containing epoxy active diluent in the cyanate ester resin matrix is E-44 or E-51, this epoxy active diluent, for carrying out chemical reaction with resin, also can be reacted with the epoxy group(ing) on graphene oxide surface.Can increase consistency and the bonding interface of graphene oxide and resin like this, on the one hand.Its viscosity is very low on the other hand, is conducive to the dispersion of graphene oxide.In addition, contain a large amount of active function groups epoxy group(ing) in graphene oxide surface grafting hyperbranched polyorganosiloxane, not only can improve graphene oxide dispersed in resin, also can strengthen the interface bond strength of itself and resin, be conducive to improve the mechanical property of matrix material.
The accompanying drawing explanation
Fig. 1 is graphene oxide/cyanate ester resin composite material preparation technology schema.
Embodiment
Now in conjunction with the embodiments, the invention will be further described for accompanying drawing:
Bad dispersibility due to graphene oxide in resin, and not high with the bonding strength of resin.Therefore, improve the dispersiveness of graphene oxide in resin, key is to carry out modification to graphene oxide.One aspect of the present invention utilizes the low viscosity of hyperbranched polyorganosiloxane, the characteristics of high reaction activity to carry out modification to graphene oxide.Utilize on the other hand the epoxy modifying agent that viscosity is very low, the dispersion that both can be graphene oxide improves strong condition, again can with graphene oxide and the resin reaction of modification.After graphene oxide, epoxy active diluent and the cyanate resin alicyclic monomer that Hyperbranched polysilane is modified mixes according to certain ratio, cast molding, prepared matrix material has mechanical property.
Concrete grammar is as follows:
(1) graphite oxide of 0.1 ~ 10 part is joined in the tetrahydrofuran solution of 1 ~ 100 part of KH-560 to ultrasonic dispersion 0.5h.Then the HCl aqueous solution that to drip 1 ~ 50mL concentration be 1mol/L, after dropwising 50 ~ 80 ℃ stir 4 ~ 7h after, except the small-molecule substance generated in dereaction, obtain hyperbranched polyorganosiloxane and modify graphene oxide.
Above-mentioned graphene oxide is the graphene oxide that hyperbranched polyorganosiloxane is modified.Be that graphene oxide and γ-glycidyl ether oxygen propyl trimethoxy silicane (KH-560) form through hydrolytic condensation, the epoxy group(ing) that its surface is a large amount of, can be reacted with the cyanate resin alicyclic monomer, improve the dispersed of graphene oxide and with the interface binding intensity of resin.The principle of the graphene oxide that hyperbranched polyorganosiloxane is modified is as follows:
(2) oxidation of 0.1 ~ 10 part of hyperbranched polyorganosiloxane being modified joins in the epoxy active diluent of 5 ~ 50 parts, under the power of 40 ~ 70W, ultrasonic dispersion is after 0.5 ~ 3 hour, join 100 parts in the bisphenol A cyanate ester resin monomer of 80 ℃ of meltings, 80 ~ 120 ℃ of lower prepolymerization 15 ~ 60min, then pour in preheated mould, in the vacuum chamber of 120 ℃, vacuumize bubble removing, until there is no bubble, do not emerge, take out mould, putting into air dry oven carries out the stage and heat up to solidify, curing process is 140 ℃/2h+160 ℃/2h+180 ℃/2h, then naturally cooling, after the demoulding, obtain graphene oxide/cyanate ester resin composite material at 200 ℃ of lower aftertreatment 2h again.
Embodiment 1:
(1) graphite oxide of 0.1 ~ 10 part is joined in the tetrahydrofuran solution of 1 ~ 100 part of KH-560 to ultrasonic dispersion 0.5h.Then the HCl aqueous solution that to drip 1 ~ 50mL concentration be 1mol/L, after dropwising 50 ~ 80 ℃ stir 4 ~ 7h after, except the small-molecule substance generated in dereaction, obtain hyperbranched polyorganosiloxane and modify graphene oxide.
(2) graphene oxide of 0.1 part of hyperbranched polyorganosiloxane being modified joins in the epoxy active diluent E-44 of 10 parts, under the power of 40 ~ 70W, ultrasonic dispersion is after 0.5 ~ 3 hour, join 100 parts in the bisphenol A cyanate ester resin monomer of 80 ℃ of meltings, at 80 ~ 120 ℃ of lower prepolymerization 15 ~ 60min, then pour in preheated mould, in the vacuum chamber of 120 ℃, vacuumize bubble removing, until there is no bubble, do not emerge, take out mould, putting into air dry oven carries out the stage and heat up to solidify, curing process is 140 ℃/2h+160 ℃/2h+180 ℃/2h, then naturally cooling, after the demoulding, obtain graphene oxide/cyanate ester resin composite material at 200 ℃ of lower aftertreatment 2h again.
Embodiment 2:
(1) hyperbranched polyorganosiloxane is modified the preparation method of graphene oxide with embodiment 1.
(2) graphene oxide of 1 part of hyperbranched polyorganosiloxane being modified joins E-51 in the epoxy active diluent of 15 parts, under the power of 40 ~ 70W, ultrasonic dispersion is after 0.5 ~ 3 hour, join 100 parts in the bisphenol A cyanate ester resin monomer of 80 ℃ of meltings, at 80 ~ 120 ℃ of lower prepolymerization 15 ~ 60min, then pour in preheated mould, in the vacuum chamber of 120 ℃, vacuumize bubble removing, until there is no bubble, do not emerge, take out mould, putting into air dry oven carries out the stage and heat up to solidify, curing process is 140 ℃/2h+160 ℃/2h+180 ℃/2h, then naturally cooling, after the demoulding, obtain graphene oxide/cyanate ester resin composite material at 200 ℃ of lower aftertreatment 2h again.
Embodiment 3:
(1) hyperbranched polyorganosiloxane is modified the preparation method of graphene oxide with embodiment 1.
(2) graphene oxide of 3 parts of hyperbranched polyorganosiloxanes being modified joins in the epoxy active diluent E-44 of 20 parts, under the power of 40 ~ 70W, ultrasonic dispersion is after 0.5 ~ 3 hour, join 100 parts in the bisphenol A cyanate ester resin monomer of 80 ℃ of meltings, at 80 ~ 120 ℃ of lower prepolymerization 15 ~ 60min, then pour in preheated mould, in the vacuum chamber of 120 ℃, vacuumize bubble removing, until there is no bubble, do not emerge, take out mould, putting into air dry oven carries out the stage and heat up to solidify, curing process is 140 ℃/2h+160 ℃/2h+180 ℃/2h, then naturally cooling, after the demoulding, obtain graphene oxide/cyanate ester resin composite material at 200 ℃ of lower aftertreatment 2h again.
Embodiment 4:
(1) hyperbranched polyorganosiloxane is modified the preparation method of graphene oxide with embodiment 1.
(2) graphene oxide of 5 parts of hyperbranched polyorganosiloxanes being modified joins in the epoxy active diluent E-51 of 30 parts, under the power of 40 ~ 70W, ultrasonic dispersion is after 0.5 ~ 3 hour, join 100 parts in the bisphenol A cyanate ester resin monomer of 80 ℃ of meltings, at 80 ~ 120 ℃ of lower prepolymerization 15 ~ 60min, then pour in preheated mould, in the vacuum chamber of 120 ℃, vacuumize bubble removing, until there is no bubble, do not emerge, take out mould, putting into air dry oven carries out the stage and heat up to solidify, curing process is 140 ℃/2h+160 ℃/2h+180 ℃/2h, then naturally cooling, after the demoulding, obtain graphene oxide/cyanate ester resin composite material at 200 ℃ of lower aftertreatment 2h again.
Claims (1)
1. a graphene oxide/cyanate ester resin composite material, is characterized in that the massfraction of material component is: 0.1～10 part of graphene oxide, 5～50 epoxy active diluents and 100 parts of bisphenol A cyanate ester resin monomer that hyperbranched polyorganosiloxane is modified; The chemical substance structure formula of the graphene oxide that described hyperbranched polyorganosiloxane is modified is:
The chemical substance structure formula of bisphenol A cyanate ester resin monomer is:
Described epoxy active diluent is E-44 or E-51;
Preparation process is as follows:
Step 1: the graphite oxide of 0.1～10 part is joined in the tetrahydrofuran solution of 1～100 part of KH-560, drip the HCl aqueous solution that 1～50mL concentration is 1mol/L after ultrasonic dispersion 0.5h, then after 50～80 ℃ of stirring 4～7h, obtain hyperbranched polyorganosiloxane and modify graphene oxide;
Step 2: 0.1～10 part of hyperbranched polyorganosiloxane is modified in the epoxy active diluent that graphene oxide joins 5～50 parts, under the power of 40～70W, ultrasonic dispersion is after 0.5～3 hour, join 100 parts in the bisphenol A cyanate ester resin monomer of 80 ℃ of meltings, at 80～120 ℃ of lower prepolymerization 15～60min;
Step 3: pour in preheated mould, in the vacuum chamber of 120 ℃, after vacuumizing bubble removing, take out, then putting into air dry oven carries out the stage and heat up to solidify, curing process is 140 ℃/2h+160 ℃/2h+180 ℃/2h, then naturally cooling, after the demoulding, then obtain graphene oxide/cyanate ester resin composite material at 200 ℃ of lower aftertreatment 2h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210282395 CN102775786B (en) | 2012-08-09 | 2012-08-09 | Graphene oxide/cyanate ester composite material and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201210282395 CN102775786B (en) | 2012-08-09 | 2012-08-09 | Graphene oxide/cyanate ester composite material and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102775786A CN102775786A (en) | 2012-11-14 |
| CN102775786B true CN102775786B (en) | 2013-12-25 |
Family
ID=47120903
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201210282395 Expired - Fee Related CN102775786B (en) | 2012-08-09 | 2012-08-09 | Graphene oxide/cyanate ester composite material and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102775786B (en) |
Families Citing this family (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9583358B2 (en) | 2014-05-30 | 2017-02-28 | Samsung Electronics Co., Ltd. | Hardmask composition and method of forming pattern by using the hardmask composition |
| KR102287343B1 (en) * | 2014-07-04 | 2021-08-06 | 삼성전자주식회사 | Hardmask composition and method of forming patterning using the hardmask composition |
| KR102287344B1 (en) | 2014-07-25 | 2021-08-06 | 삼성전자주식회사 | Hardmask composition and method of forming patterning using the hardmask composition |
| CN104231624B (en) * | 2014-08-22 | 2016-05-11 | 南京信息职业技术学院 | A kind of modified cyanic acid ester resin heat-conductive composite material and preparation method thereof |
| CN104312147B (en) * | 2014-10-23 | 2016-11-23 | 南京信息职业技术学院 | A kind of ZnOw/graphene nanometer sheet modified synergic cyanate ester resin heat-conductive composite material and preparation method thereof |
| KR102384226B1 (en) | 2015-03-24 | 2022-04-07 | 삼성전자주식회사 | Hardmask composition and method of forming pattern using the same |
| KR102463893B1 (en) | 2015-04-03 | 2022-11-04 | 삼성전자주식회사 | Hardmask composition and method of forming patterning using the hardmask composition |
| CN105037801B (en) * | 2015-08-03 | 2018-01-16 | 苏州大学 | A kind of phosphorous hydridization graphene oxide and preparation method thereof |
| CN105061760B (en) * | 2015-08-03 | 2017-10-13 | 苏州大学 | A kind of phosphorous hydridization graphene oxide modified cyanic acid ester resin and preparation method thereof |
| CN106008935A (en) * | 2016-06-21 | 2016-10-12 | 青岛志卓通力新材料有限公司 | Preparation method for graphene modified unsaturated resin |
| CN108165006B (en) * | 2016-12-07 | 2020-10-16 | 航天特种材料及工艺技术研究所 | Graphene modified cyanate ester resin and preparation method thereof |
| CN108219455A (en) * | 2016-12-15 | 2018-06-29 | 中国航空工业集团公司济南特种结构研究所 | A kind of polymer matrix composite |
| CN106893322B (en) * | 2017-04-01 | 2019-03-08 | 国家纳米科学中心 | A kind of graphene/cyanate composite material and its preparation method and application |
| US11034847B2 (en) | 2017-07-14 | 2021-06-15 | Samsung Electronics Co., Ltd. | Hardmask composition, method of forming pattern using hardmask composition, and hardmask formed from hardmask composition |
| KR102433666B1 (en) | 2017-07-27 | 2022-08-18 | 삼성전자주식회사 | Hardmask composition, method of forming patterning using the hardmask composition, and hardmask formed from the hardmask composition |
| KR102486388B1 (en) | 2017-07-28 | 2023-01-09 | 삼성전자주식회사 | Method of preparing graphene quantum dot, hardmask composition including the graphene quantum dot obtained by the method, method of forming patterning using the hardmask composition, and hardmask formed from the hardmask composition |
| CN108329468A (en) * | 2018-02-02 | 2018-07-27 | 中国科学院大学 | A kind of preparation method of electromagnetic shielding composite material |
| CN110229464A (en) * | 2019-05-11 | 2019-09-13 | 常州宝利美石墨烯有限公司 | A kind of epoxy silicon oil modified graphene oxide and epoxy resin composite material preparation method |
| CN113789118A (en) * | 2021-08-25 | 2021-12-14 | 浙江儒商科技有限公司 | Preparation method of cyanate ester wear-resistant self-lubricating swash plate |
| CN115124835B (en) * | 2022-09-01 | 2022-12-06 | 深圳市板明科技股份有限公司 | High-humidity-heat-resistant hole plugging resin and resin hole plugging method |
| CN116003812A (en) * | 2022-12-01 | 2023-04-25 | 东莞市佳迪新材料有限公司 | Cyclic silicon-containing hydrogen bond crosslinking agent, sealant composition containing cyclic silicon-containing hydrogen bond crosslinking agent and preparation method of sealant composition |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812194A (en) * | 2010-03-17 | 2010-08-25 | 湖北大学 | Graphene-based barrier composite material and preparation method thereof |
-
2012
- 2012-08-09 CN CN 201210282395 patent/CN102775786B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101812194A (en) * | 2010-03-17 | 2010-08-25 | 湖北大学 | Graphene-based barrier composite material and preparation method thereof |
Non-Patent Citations (6)
| Title |
|---|
| Cyanate ester resin/grapheme nanocomposite:curing dynamics and network formation;Xiao Wang,et al.;《European polymer journal》;20120404;第48卷;第1035页，第1040页图9 * |
| E-51环氧树脂改性双酚A型氰酸酯树脂的研究;马万翔等;《热固性树脂》;20110131;第26卷(第1期);第6页第2段，第7页第4段，第8页式1 * |
| KH-570功能化石墨烯的制备与表征;时镜镜等;《无机化学学报》;20120131;第28卷(第1期);第132页左栏第2段 * |
| Xiao Wang,et al..Cyanate ester resin/grapheme nanocomposite:curing dynamics and network formation.《European polymer journal》.2012,第48卷 |
| 时镜镜等.KH-570功能化石墨烯的制备与表征.《无机化学学报》.2012,第28卷(第1期), |
| 马万翔等.E-51环氧树脂改性双酚A型氰酸酯树脂的研究.《热固性树脂》.2011,第26卷(第1期), |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102775786A (en) | 2012-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102775786B (en) | Graphene oxide/cyanate ester composite material and preparation method thereof | |
| CN106520040B (en) | A kind of modified graphene oxide, MGO-SiO2Nano-hybrid material and MGO-SiO2The preparation method of phenol-formaldehyde resin modified hot melt adhesive film | |
| CN102796374B (en) | Carbon nanotube/benzoxazine/bimaleimide composite material and preparation method thereof | |
| CN102443247B (en) | Preparation method of graphene oxide grafted POSS (polyhedral oligomeric silsesquioxane) modified epoxy resin | |
| CN104164208B (en) | A kind of preparation method of Graphene/polyimides composite adhesive | |
| CN102796373B (en) | Graphene/cyanate ester/bimaleimide composite material and preparation method thereof | |
| CN102746473B (en) | Method for preparing hyperbranched polysiloxane grafted carbon nanotube containing active double bonds | |
| CN103965590B (en) | Epoxy resin composite material of a kind of coordination plasticizing and preparation method thereof | |
| CN102516774B (en) | Preparation method of modified silicon resin matrix and application of the modified silicon resin matrix | |
| CN104231624A (en) | Modified cyanate resin heat-conducting composite material and preparation method thereof | |
| CN102079874A (en) | Preparation method of cage-type silsesquioxane-containing low-dielectric cyanate hybrid resin | |
| CN105820276A (en) | Preparation method of ultrahigh-conductivity graphene modified polymethyl methacrylate composite material | |
| CN109265930A (en) | A kind of low-cost high-toughness self-lubricating epoxy resin and preparation method | |
| CN103992620A (en) | Microcellular foaming epoxy resin matrix material with high performance and preparation method thereof | |
| CN102504200A (en) | High-performance high-heat-resistance modified epoxy resin and preparation method and use thereof | |
| CN101250317A (en) | Preparation method of epoxy resin composite material with surface modified spherical SiO2 particles | |
| CN101891936B (en) | Preparation method of composite material based on epoxy resin and phosphazene nanotubes | |
| CN109180947A (en) | One kind modified bismaleimide resin containing ethenyl cage model sesquialter siloxane and preparation method | |
| CN103694632A (en) | Preparation method of epoxy resin composite material | |
| CN106867202A (en) | A kind of composition epoxy resin | |
| CN101864076A (en) | Cyanate resin modified by phenylacetylene base silane resin and preparation method thereof | |
| CN109836557A (en) | Toughened hydrophobic epoxy resin and preparation method thereof | |
| CN106590499A (en) | Epoxy resin glue solution with high peel strength for copper-clad plate and preparation method of glue solution | |
| CN113004655A (en) | Preparation method of glass fiber reinforced thermosetting resin prepreg | |
| CN102430373B (en) | Preparation method of organosilicon hollow microsphere |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20131225 Termination date: 20150809 |
|
| EXPY | Termination of patent right or utility model |